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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 73 records · Page 4
All sourcesNASA NTRSDOE OSTI
NASA NTRS1987

Methane oxidation and methane fluxes in the ocean surface layer and deep anoxic waters

Measured biological oxidation rates of methane in near-surface waters of the Cariaco Basin are compared with the diffusional fluxes computed from concentration gradients of methane in the surface layer. Methane fluxes and oxidation rates were investigated in surface waters, at the oxic/anoxic interface, and in deep anoxic waters. It is shown that the surface-waters oxidation of methane is a mechanism which modulates the flux of methane from marine waters to the atmosphere.

Ward, B. B.↗
DOE OSTI2020

Field-assisted suppression of coke in the methane steam reforming reaction

Electric fields were applied to an unsupported nickel catalyst during methane steam reforming with a low steam-to-methane ratio of 2:1. As expected, catalysts operated in standard mode (without an applied field) experienced high levels of coking. Coke formation was almost completely suppressed by the application of a positive electric field. This is explained using density functional theory computations which indicate that positive electric fields (1) increase the affinity for water adsorption on the surface, thereby increasing the amount of oxygen available to remove carbon, (2) stabilize individual carbon fragments, thus reducing their tendency to polymerize, and (3) increase the oxygen storage capabilities of the catalyst by inducing sub-surface oxygen formation and bulk oxidation.

Gray, Jake T.↗
DOE OSTI2018

Rational Design of a Catalyst for the Selective Monoborylation of Methane

Combined computational and experimental studies elucidate the mechanism and suggest rational design and optimization strategies of a bis(phosphine)-supported iridium-catalyst for methane monoborylation. The activation of the C–H bond in methane via oxidative addition using tris(boryl) iridium(III) complexes bearing bis-chelating supporting ligands is modeled computationally. This model shows that the use of the soft Lewis base ligand such as 1,2-bis(dimethylphosphino)ethane (dmpe) lowers the activation barrier of the rate-determining step as it facilitates polarization of the metal-center, lowering the barrier of the oxidative addition to afford a seven-coordinate iridium(V) intermediate. The experimental optimization of this reaction using high-throughput methods shows that up to 170 turnovers can be achieved at 150 °C (500 psi) within 16 h using bis(pinacolato)diboron, a well-defined homogeneous and monomeric catalyst (dmpe)Ir(COD)Cl that is readily available from commercial precursors, with selectivity for the monoborylation product. High-boiling cyclic aliphatic solvents decalin and cyclooctane also prove suitable for this reaction, while being inert toward borylation. In accordance with the lower calculated activation barrier, catalytic turnover is also observed at 120 °C with up to 50 turnovers over the course of 4 days in cyclohexane solvent. Here, it was found that the borylation of methane is only achieved via one catalytic cycle, and buildup of pinacolborane, a side-product from methane borylation with bis(pinacolato)diboron, inhibits catalytic activity.

computational molecular modeling↗
DOE OSTI2015

Simultaneous Detection of Water, Methane, and Carbon Monoxide in the Atmosphere of Exoplanet HR 8799 b

Here, absorption lines from water, methane, and carbon monoxide are detected in the atmosphere of exoplanet HR 8799 b. A medium-resolution spectrum presented here shows well-resolved and easily identified spectral features from all three molecules across the K band. The majority of the lines are produced by CO and H 2 O, but several lines clearly belong to CH 4 . Comparisons between these data and atmosphere models covering a range of temperatures and gravities yield log mole fractions of H 2 O between –3.09 and –3.91, CO between –3.30 and –3.72, and CH 4 between –5.06 and –5.85. More precise mole fractions are obtained for each temperature and gravity studied. A reanalysis of H-band data, previously obtained at a similar spectral resolution, results in a nearly identical water abundance as determined from the K-band spectrum. The methane abundance is shown to be sensitive to vertical mixing and indicates an eddy diffusion coefficient in the range of 10 6 –10 8 cm 2 s –1 , comparable to mixing in the deep troposphere of Jupiter. The model comparisons also indicate a carbon-to-oxygen ratio (C/O) between ~0.58 and 0.7, encompassing previous estimates for a second planet in the same system, HR 8799 c. Super-stellar C/O could indicate planet formation by core-accretion; however, the range of possible C/O for these planets (and the star) is currently too large to comment strongly on planet formation. More precise values of the bulk properties (e.g., effective temperature and surface gravity) are needed for improved abundance estimates.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2023

SPRUCE Anaerobic oxidation of methane mitigates net methane production and responds to long-term experimental warming in a northern bog: Supporting data

This data set contains measurements of anaerobic oxidation of methane (AOM), net methane (CH4) production, carbon dioxide (CO2) production, and gross CH4 production measurements from the SPRUCE experiment (Hanson et al. 2017). CH4 is greenhouse gas with 45 times the sustained global warming potential of CO2 over 100 years, which may have significant implications on global climate change. The process of AOM plays a large role in the extent of CH4 emissions from wetland environments like those at the SPRUCE experiment site. This study conducted two on different dates. In experiment 1, net CH4 and CO2 production were measured with a gas chromatograph through the peat profile at in situ temperatures of the SPRUCE plots four times from May to October, 2016 (2016-05 to 2016-10). Two treatments were examined, a Porewater Treatment that was a 1:1 volumetric peat:porewater slurry and a No Porewater Treatment that was field-moist peat with no porewater added. Additionally, net CH4 production were measured at frequent intervals (from 4 hr to 9 d) in peat from selected SPRUCE plots from soil collected on October 16, 2016 (2016-10-16). Samples were collected from the SPRUCE plots, immediately made anaerobic, and transported to the University of Oregon for rate measurements within several days of collection. In experiment 2, AOM, net CH4 production, CO2 production, and gross CH4 production were measured through the peat profile at in situ field temperatures once from samples collected in July, 2021 (2021-07). The same two porewater treatments were examined. AOM was measured with a 13CH4 tracer method using a Picarro G2201-i analyzer for isotopic CO2/CH4 quantification with a small stable isotope module attached. This data set contains three data files in comma separate (*.csv) format. This data set is associated with the following publication: Barney, M, AM Hopple, LL Gregory, JK Keller, and SD Bridgham. 2024. Anaerobic oxidation of methane mitigates net methane production and responds to long-term experimental warming in a northern bog. Soil Biology and Biochemistry, 190, 109316. https://doi.org/10.1016/j.soilbio.2024.109316.

SPRUCE Experiment, Marcell Experimental Forest, Me↗
DOE OSTI2018

A modular approach for high-flux lactic acid production from methane in an industrial medium using engineered Methylomicrobium buryatense 5GB1

Abstract Convergence of market drivers such as abundant availability of inexpensive natural gas and increasing awareness of its global warming effects have created new opportunities for the development of small-scale gas-to-liquid (GTL) conversion technologies that can efficiently utilize methane, the primary component of natural gas. Leveraging the unique ability of methanotrophs that use methane as carbon and energy source, biological GTL platforms can be envisioned that are readily deployable at remote petroleum drilling sites where large chemical GTL infrastructure is uneconomical to set-up. Methylomicrobium buryatense, an obligate methanotroph, has gained traction as a potential industrial methanotrophic host because of availability of genetic tools and recent advances in its metabolic engineering. However, progress is impeded by low strain performance and lack of an industrial medium. In this study, we first established a small-scale cultivation platform using Hungate tubes for growth of M. buryatense at medium-to-high-throughput that also enabled 2X faster growth compared to that obtained in traditional glass serum bottles. Then, employing a synthetic biology approach we engineered M. buryatense with varying promoter (inducible and constitutive) and ribosome-binding site combinations, and obtained a strain capable of producing l-lactate from methane at a flux 14-fold higher than previously reported. Finally, we demonstrated l-lactate production in an industrial medium by replacing nitrate with less-expensive ammonium as the nitrogen source. Under these conditions, l-lactate was synthesized at a flux approximately 50-fold higher than that reported previously in a bioreactor system while achieving a titer of 0.6 g/L. These findings position M. buryatense closer to becoming an industrial host strain of choice, and pave new avenues for accelerating methane-to-chemical conversion using synthetic biology.

Garg, Shivani↗
DOE OSTI2020

Experimental Insights into the Coupling of Methane Combustion and Steam Reforming in a Catalytic Plate Reactor in Transient Mode

The microstructured reactor concept is very promising technology to develop a compact reformer for distributed hydrogen generation. In this work, a catalytic plate reactor (CPR) is developed and investigated for the coupling of methane combustion (MC) and methane steam reforming (MSR) over Pt/Al 2 O 3 -coated microchannels in cocurrent and counter-current modes in transient experiments during start-up. A three-dimensional (3D) computational fluid dynamics (CFD) simulation shows uniform velocity and pressure distribution profiles in microchannels. For a channel velocity from 5.1 to 57.3 m/s in the combustor, the oxidation of methane is complete and self-sustainable without explosion, blow-off, or extinction; nevertheless, flashbacks are observed in counter-current mode. In the reformer, the maximum methane conversion is 84.9% in cocurrent mode, slightly higher than that of 80.2% in counter-current mode at a residence time of 33 ms, but at the cost of three times higher energy input in the combustor operating at ~1000 °C. Nitric oxide (NO) is not identified in combustion products, but nitrous oxide (N 2 O) is a function of coupling mode and forms significantly in cocurrent mode. Furthermore, this research would be helpful to establish the start-up strategy and environmental impact of compact reformers on a small scale.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Single-Step Selective Oxidation of Methane by Iron-Oxo Species in the Metal–Organic Framework MFU-4l

The direct and selective conversion of methane to methanol can be considered a holy grail for catalysis research. In this work, we study a metal-organic framework known as MFU-4l, modified by design to include highly reactive iron-oxo species for the catalytic C-H bond activation of methane. We investigate the oxidation of methane and the further potential oxidation of the product methanol using N 2 O as an oxygen source and map the potential energy landscape of these reactions using density functional theory calculations. We show that the highest energy barrier encountered during the methane oxidation process is not the C-H bond breaking, but the activation of the iron center by N 2 O. Furthermore, the potential energy landscape for the C-H bond activation exhibits a large, high-energy plateau region instead of a sharp transition state, thus differing from the traditional radical rebound mechanism. Furthermore, this insight offers interesting potential routes to enhance the catalytic activity of the catalyst, to hinder unwanted deactivation pathways, and to reduce the activity towards the over-oxidation of the product.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Computational Screening of Supported Metal Oxide Nanoclusters for Methane Activation: Insights into Homolytic versus Heterolytic C–H Bond Dissociation

Since its discovery in zeolites, the [CuOCu] 2+ motif has played an important role in our understanding of selective methane activation over supported metal oxide nanoclusters. Although there are two known C-H bond dissoci-ation mechanisms, namely homolytic and heterolytic cleavage, most computational studies on optimizing metal oxide nanoclusters for improved methane activation reactivity have focused only on the homolytic mechanism. In this work, both mechanisms were examined for a set of 21 mixed metal oxide complexes of the form of [M 1 OM 2 ] 2+ (M 1 , M 2 = Mn, Fe, Co, Ni, Cu, Zn). Except for pure copper, heterolytic cleavage was found to be the dominant C-H bond activation pathway for all systems. Furthermore, mixed systems including [CuOMn] 2+ , [CuONi] 2+ , and [CuOZn] 2+ are predicted to possess similar methane activation activity as pure [CuOCu] 2+ . Furthermore, these results suggest that both homolytic and heterolytic mechanisms should be considered in computing methane activation energies on supported metal oxide nanoclusters.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Interaction of Hydrocarbons with Clays under Reservoir Conditions: In Situ Infrared and Nuclear Magnetic Resonance Spectroscopy and X-ray Diffraction for Expandable Clays with Variably Wet Supercritical Methane

The results from novel in situ high-pressure nuclear magnetic resonance (NMR) spectroscopy, infrared (IR) spectroscopy, and X-ray diffraction (XRD) investigation of the interaction of the smectite hectorite with variably wet supercritical methane (scCH4) at 90 bar and 323 K (hydrostatic conditions equivalent to ~1 km depth) show that CH4 occurs in the clay interlayers, in pores external to the individual clay particles, and as bulk fluid. The occupancy of each environment depends on the relative humidity (RH) of the CH4-rich fluid and the hydration energy and size of the charge-balancing cation. As RH increases, the fraction of interlayer and interparticle CH4 decreases, although with Cs+, addition of a small amount of H2O initially increases CH4 uptake. Maximum interlayer CH4 adsorption occurs when the mean basal spacing just permits methane intercalation (~11.5 Å) and never below this basal spacing. It is also higher with divalent cations than with monovalent cations. The data show that CH4 adsorption occurs predominantly via a weak dispersion interaction with the clay and that its intercalation occurs via a passive space-filling hydrophobic mechanism. The results suggest that, under reservoir conditions, smectite interlayers may provide a reservoir for CH4 under low-water conditions.

Bowers, Geoffrey M.↗
DOE OSTI2021

Catalytic decomposition of methane into hydrogen and high-value carbons: combined experimental and DFT computational study

Thermocatalytic decomposition (TCD) of methane can produce hydrogen and valuable nanocarbon co-products with low to near-zero CO2 emission. In this study, a series of Pd promoted Ni catalysts, prepared with various Ni/Pd ratios on a CNT support, were evaluated for methane TCD performance. Characterization and calculations using density functional theory (DFT) were carried out to elucidate the activity–structure relationship and growth mechanism of carbon nanomaterials. It was found that the methane conversion and stability of the catalysts were highly dependent on the Ni/Pd ratio and reaction temperature. DFT calculations revealed that the diffusion of carbon in the metal sublayer required for CNT growth was more favorable in the Ni–Pd alloy lattice suggesting that the buildup of carbon in the metal alloy sublayer facilitated the formation of CNTs and CNFs. A cyclic reaction–regeneration process for self-sustained TCD was experimentally demonstrated. In each cycle, a portion of the separated CNT product was used to re-synthesize the Ni–Pd/CNT catalyst for use in the next reaction cycle. After five cycles of operation, the CH4 conversion, morphology and crystallinity of the carbon product remained unchanged.

Wang, I-Wen↗
DOE OSTI2022

Developing reactors for electrifying bio-methanation: a perspective from bio-electrochemistry

The integration of microbial synthesis with renewable electricity is an emerging route for both CO 2 utilization and seasonal energy storage in the form of stored bio-electrofuels. The major benefits of electrifying bioreactors include: using highly selective bio-catalysts for CO 2 conversion under mild reaction conditions; decoupling the production of more facile electrochemical intermediates, such as hydrogen, at the electrode from the production of bio-catalyzed multi-electron and/or carbon products, such as methane or acetate; using microbes as robust and self-regenerating catalysts enabling higher efficiency and durability in CO 2 conversion systems compared to inorganic catalysis. In this Perspective, we propose research aimed at developing electro-bioreactor components that will increase the productivity of the reactor while maintaining high energy efficiency and biocompatible reaction conditions to fully realize the benefits of electrified bioreactors. Furthermore, these developments include: flow reactors with tailored 3D electrodes to optimally use the reactor volume, electrocatalysts designed for peak performance in neutral pH electrolytes, high conductivity microbial media, and new membrane separator materials with high ion conductivity and low gas permeability. Production of methane via a hybrid electrical-biological approach is taken as a case study to motivate these developments. Finally, an iterative design–manufacture–test cycle, enabled by additive manufacturing and 3D printing technologies, is proposed to rapidly prototype components prior to large-scale manufacturing.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗